CN113603827B - Machine-made sand regulator of alcohol ether modified carboxylic acid polymer and preparation method thereof - Google Patents
Machine-made sand regulator of alcohol ether modified carboxylic acid polymer and preparation method thereof Download PDFInfo
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- CN113603827B CN113603827B CN202110843153.2A CN202110843153A CN113603827B CN 113603827 B CN113603827 B CN 113603827B CN 202110843153 A CN202110843153 A CN 202110843153A CN 113603827 B CN113603827 B CN 113603827B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/46—Water-loss or fluid-loss reducers, hygroscopic or hydrophilic agents, water retention agents
- C04B2103/465—Water-sorbing agents, hygroscopic or hydrophilic agents
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Polyethers (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a machine-made sand regulator of alcohol ether modified carboxylic acid polymer and a preparation method thereof, firstly, 75-91 parts of carboxylic acid monomer acid, 33-67 parts of alcohol ether monomer, 2-4 parts of chain transfer agent, 0.1-0.3 part of polymerization inhibitor and water are added into a reaction kettle provided with a stirrer; heating to 80-90 deg.C in water bath; then 150-175 parts of carboxylic acid monomer, 0.1-0.3 part of polymerization inhibitor and 187 parts of 178-187 parts of water are prepared into solution A, 1.64-3.21 parts of initiator, 2-8 parts of chain transfer agent and water are prepared into solution B, A, B is dripped into the reaction kettle by a dripping pump, wherein the dripping of the solution A is 1-1.5 hours, and the dripping of the solution B is 1-2 hours. And after the A, B liquid is dripped, preserving heat for 1-2 hours, cooling and discharging, and supplementing water to 1000 parts to prepare the machine-made sand regulator. According to the invention, the length and flexibility of a side chain of a polymer molecular chain are increased by introducing an alcohol ether monomer, and the dispersion performance of the polymer is improved, so that the polymer can be adapted to machine-made sand with different grades, and the service performance of the machine-made sand is improved.
Description
Technical Field
The invention belongs to the technical field of engineering construction, and particularly relates to a machine-made sand regulator of an alcohol ether modified carboxylic acid polymer and a preparation method thereof.
Background
At present, the engineering and building industry has a large demand for gravels, but at present, the resource of natural sand is in shortage, the national ecological environment protection is more and more emphasized, the consumption of the natural sand is gradually reduced, and the preparation of concrete by using machine-made sand instead of the natural sand becomes a necessary trend of industry development. However, machine-made sand has the defects of clear edges and corners, rough surface, poor gradation and the like, so that the workability of concrete mixed by the machine-made sand is poor, and few people can provide an effective solution at present. Therefore, the development of a novel machine-made sand regulator becomes a research hotspot in the engineering and construction industry at the present stage.
The invention discloses self-compacting light aggregate machine-made sand concrete and a preparation method thereof, and the invention discloses self-compacting light aggregate machine-made sand concrete, which comprises the following components in parts by weight: the concrete comprises, by weight, 260-330 cement-containing materials, 140-160 fly ash-containing materials, 30-40 mineral powder, 20-40 silica fume, 420-500 machine-made sand-containing materials, 100-110 light sand-containing materials, 360-400 light aggregate-containing materials, 150 water-containing materials, 160.8-8.3 water reducing agents, 0.45-2.8 slump retaining agents and 0.18-0.22 air entraining agents, wherein the slump retaining agents are obtained by compounding isopentenol polyoxyethylene ether TPEG, acrylic acid and composite molecular weight regulators, the air entraining agents are rosin soap air entraining agents and are obtained by compounding rosin, caustic soda, triethanolamine and sodium dodecyl sulfate.
The embodiment of the invention provides a machine-made sand regulator and a preparation method thereof, wherein the machine-made sand regulator contains a polycarboxylic acid water reducing agent, a glue reducing agent, an early strength agent, an air entraining agent, a polyether type defoaming agent, a compact repairing agent, a viscosity thixotropic agent and water, is suitable for machine-made sand with different grades, can control the better working performance of concrete and can ensure the durability requirement of the concrete at the same time, the machine-made sand regulator provided by the invention can ensure that various detection indexes of newly-mixed concrete are obviously superior to those of common additives in the current market, the slump of the concrete is as high as 200mm, the volume weight of the newly-mixed concrete reaches 2438kg/m3, the activity and the 28d strength reaches 66.8MPa, and the strength increment is increased by over 30 percent compared with the common additives.
The patent CN110357487A discloses a machine-made sand regulator and application thereof in machine-made sand-containing concrete, and the invention discloses a machine-made sand regulator and application thereof in machine-made sand-containing concrete, wherein the machine-made sand regulator comprises the following raw materials in parts by weight: 10-15% of diethanol monoisopropanolamine, 2-5% of maltodextrin, 5-10% of dipropylamine, 1-3% of air entraining agent for Kelaien polyether concrete, 5-10% of sodium hexametaphosphate and the balance of water, wherein the maltodextrin is prepared by using various starches as raw materials and performing low-degree controlled hydrolysis conversion by an enzymatic process, purification and drying, wherein the hydrolysis DE value of the maltodextrin is below 20%, and the molecular formula of the dipropylamine is C6H15N or (CH3CH2CH2)2 NH; molecular weight 101.19; a colorless liquid with an ammonia odor; can be mixed and dissolved in ethanol, diethyl ether, benzene and acetone; a flammable liquid; the main application is as follows: organic synthesis intermediates, and as solvents. The machine-made sand regulator has the advantages of simple process, convenient operation, no waste in the production process, environmental protection, reliability and contribution to large-scale industrial production, and can effectively improve the strength of concrete, reduce the consumption of rubber materials, regulate the wrapping property of the concrete and increase the fluidity of the concrete when in use.
Different from the patents, the invention aims to prepare the machine-made sand regulator of the alcohol ether modified carboxylic acid polymer. According to the invention, long-chain alcohol ether monomers are used for modifying the machine-made sand regulator of carboxylic acids, ether bonds are introduced on the molecular chain of the regulator, so that a certain hydrophilic property is provided for the regulator, a good water retention effect is achieved when concrete is mixed, the segregation phenomenon of the concrete is reduced, the workability of the concrete is improved, the machine-made sand particles can be better dispersed, the internal structure of the concrete is improved, and the strength is improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a machine-made sand regulator of an alcohol ether modified carboxylic acid polymer. The preparation method has the advantages of simple preparation process, excellent product performance, good stability and wide adaptability.
According to the invention, the alcohol ether modified carboxylic acid polymer is prepared by taking carboxylic acid monomers and alcohol ether monomers as raw materials through a polymerization reaction, hydroxyl and ether bonds in the alcohol ether monomers can provide a better dispersing effect for regulator molecules, the dispersing degree of machine-made sand in concrete can be improved, the workability of the concrete is improved, and segregation is avoided. Hydroxyl groups in the alcohol ether can complex calcium ions in the cement, delay cement hydration, have a certain retarding effect, can improve the conveying performance of the concrete, delay the release of hydration heat and improve the later strength of the concrete.
The technical scheme of the invention is as follows:
the preparation method of the machine-made sand regulator of the alcohol ether modified carboxylic acid polymer is characterized by sequentially comprising the following operation steps of:
the method comprises the following steps: adding 75-91 parts of carboxylic acid monomer acid, 33-67 parts of alcohol ether monomer, 2-4 parts of chain transfer agent, 0.1-0.3 part of polymerization inhibitor and water into a reaction kettle with a stirrer in parts by mass; heating to 80-90 deg.C in water bath;
step two: 150-175 parts of carboxylic acid monomer, 0.1-0.3 part of polymerization inhibitor and 187 parts of 178-187 parts of water are prepared into solution A, 1.64-3.21 parts of initiator, 2-8 parts of chain transfer agent and water are prepared into solution B, A, B is dripped into the reaction kettle by a dripping pump, wherein the dripping of the solution A is 1-1.5 hours, and the dripping of the solution B is 1-2 hours. And after the A, B liquid is dripped, preserving heat for 1-2 hours, cooling and discharging, and supplementing water to 1000 parts to prepare the machine-made sand regulator.
The carboxylic acid monomer is one or more of maleic acid and itaconic acid. The preferable mass ratio is 3: 2 maleic acid and itaconic acid.
The alcohol ether monomer is any one or more of allyl hydroxyethyl ether and monomethyl allyl glycol ether. The preferable mass ratio is 3: 4 and monomethylallyl glycol ether.
The initiator is any one or more of ammonium persulfate, azobisisobutyronitrile, diisopropyl peroxydicarbonate, Benzoyl Peroxide (BPO), di-tert-butyl peroxide (DTBP) and dicyclohexyl peroxydicarbonate. The preferable mass ratio is 1: 1 ammonium persulfate and benzoyl peroxide.
The polymerization inhibitor is hydroquinone, p-tea quinone, p-benzoquinone, p-tert-butyl catechol, 2, 6-di-tert-butyl p-methyl phenol, 4,4' -di-tert-butyl biphenyl and 1, 1-diphenyl-2-trinitrophenylhydrazine, preferably the mass ratio is 1: 2 and 1, 1-diphenyl-2-trinitrophenylhydrazine.
The chain transfer agent is any one or more of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and mercaptopropanol. Preferably a composition of mercaptopropionic acid and mercaptoethanol in a mass ratio of 2: 1.
The machine-made sand regulator of the alcohol ether modified carboxylic acid polymer is polymerized by the following components, the total mass of the raw materials is 1000 parts, and the components comprise:
225-266 parts of carboxylic acid monomer;
33-67 parts of alcohol ether monomer;
1.64-3.21 parts of an initiator;
0.2-0.6 part of polymerization inhibitor;
4-12 parts of a chain transfer agent;
the balance of water.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. the hydroxyl is introduced into the molecular chain of the machine-made sand regulator, has the capability of complexing calcium ions, has a certain retardation effect in concrete, can delay the release of hydration heat of the concrete, reduces drying shrinkage, and improves the later strength of the concrete.
2. In the preparation process, a small amount of polymerization inhibitor is added, so that the molecular chain of the polymer is shortened, and the polymer with small molecular chains is adsorbed on the surface of the machine-made sand particles without winding to reduce the action rate of the regulator. The regulator of the invention can be suitable for machine-made sand of various grades and has good effect.
3. The ether bond in the alcohol ether monomer used in the invention can play a good steric hindrance role, can disperse machine-made sands with different gradations, and has a certain water retention property, can adsorb water molecules in concrete to form a water film, plays a role in lubricating concrete particles, and improves the fluidity of the concrete.
Detailed Description
The following examples further describe embodiments of the present invention in detail. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The machine-made sand regulator of the alcohol ether modified carboxylic acid polymer is prepared from the following components:
and (3) mass ratio: 2 259 parts of a composition of maleic acid and itaconic acid;
the mass ratio is 3: 49 parts of allyl hydroxyethyl ether and monomethylallyl glycol ether of 4;
the mass ratio is 1: 2.20 parts of the composition of ammonium persulfate and benzoyl peroxide of 1;
the mass ratio is 1: 0.4 part of a composition of p-benzoquinone 2 and 1, 1-diphenyl-2-trinitrophenylhydrazine;
8 parts of a composition of mercaptopropionic acid and mercaptoethanol in a mass ratio of 2: 1;
the balance of water, the total mass is 1000 parts.
The preparation method comprises the following steps:
the method comprises the following steps: adding 86 parts of a mixture of 3: 2, and 49 parts of a composition of maleic acid and itaconic acid, wherein the mass ratio is 3: 4 of allyl hydroxyethyl ether and monomethyl allyl glycol ether, 2 parts of a composition of mercaptopropionic acid and mercaptoethanol in a mass ratio of 2:1, 0.1 part of a mixture of allyl hydroxyethyl ether and monomethyl allyl glycol ether in a mass ratio of 1: 2 p-benzoquinone and 1, 1-diphenyl-2-trinitrophenylhydrazine, and water. The mixture was heated to 85 ℃ using a water bath.
Step two: mixing 173 parts of a mixture of 3: 2, 0.3 parts of a composition of maleic acid and itaconic acid, and a mass ratio of 1: 2 and a composition of p-benzoquinone and 1, 1-diphenyl-2-trinitrophenylhydrazine and water are prepared into a solution A, and 2.20 parts by mass of the composition is as follows: 1, 6 parts of a composition of ammonium persulfate and benzoyl peroxide, 6 parts of a composition of mercaptopropionic acid and mercaptoethanol in a mass ratio of 2:1 and water are prepared into a solution B, A, B is dripped into a reaction kettle by using a dripping pump, wherein the dripping of the solution A is 1.3 hours, and the dripping of the solution B is 1.5 hours. And after the A, B liquid is dripped, preserving heat for 1 hour, cooling and discharging, and supplementing water to 1000 parts to prepare the machine-made sand regulator.
The processes of examples 2 to 6 are the same as in example 1, and the differences in the components and the differences in the process parameters are shown in tables 1 and 2.
Table 1 shows the difference in the components of the preparation methods of examples 1 to 6 of the present invention
Table 2 shows the difference between the process parameters of the preparation methods of examples 1 to 6 of the present invention
And (3) detecting data:
the embodiment of the invention and a CS-06 concrete mechanism sand regulator of Guangzhou I and building materials are used for modifying mechanism sand to prepare a C50 concrete sample, and the following table is obtained through detection.
According to the detection data in the table, the machine-made sand regulator can better improve the performance of the machine-made sand, so that the prepared concrete has better strength and fluidity.
The above embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various combinations, modifications or equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered by the claims of the present invention.
Claims (5)
1. The preparation method of the machine-made sand regulator of the alcohol ether modified carboxylic acid polymer is characterized by sequentially comprising the following operation steps of:
the method comprises the following steps: adding 75-91 parts of carboxylic acid monomer acid, 33-67 parts of alcohol ether monomer, 2-4 parts of chain transfer agent, 0.1-0.3 part of polymerization inhibitor and water into a reaction kettle with a stirrer in parts by mass; heating to 80-90 deg.C in water bath;
step two: preparing 150-175 parts of carboxylic acid monomer, 0.1-0.3 part of polymerization inhibitor and 187 parts of 178-187 parts of water into solution A, preparing 1.64-3.21 parts of initiator, 2-8 parts of chain transfer agent and water into solution B, and dropwise adding A, B into the reaction kettle by using a dropwise adding pump, wherein the dropwise adding of the solution A is carried out for 1-1.5 hours, and the dropwise adding of the solution B is carried out for 1-2 hours; after the A, B liquid is dripped, preserving heat for 1-2 hours, cooling and discharging, and supplementing water to 1000 parts to prepare the machine-made sand regulator;
the carboxylic acid monomer is itaconic acid and/or maleic acid;
the alcohol ether monomer is allyl hydroxyethyl ether and/or monomethyl allyl glycol ether.
2. The preparation method of the machine-made sand regulator of alcohol ether modified carboxylic acid polymers as claimed in claim 1, characterized in that: the initiator is any one or more of ammonium persulfate, azobisisobutyronitrile, diisopropyl peroxydicarbonate, benzoyl peroxide, di-tert-butyl peroxide and dicyclohexyl peroxydicarbonate.
3. The preparation method of the machine-made sand regulator of alcohol ether modified carboxylic acid polymers as claimed in claim 1, characterized in that: the polymerization inhibitor is any one or more of hydroquinone, p-gao quinone, p-benzoquinone, p-tert-butyl catechol, 2, 6-di-tert-butyl-p-methylphenol and 1, 1-diphenyl-2-trinitrophenylhydrazine.
4. The preparation method of the machine-made sand regulator of alcohol ether modified carboxylic acid polymers as claimed in claim 1, characterized in that: the chain transfer agent is any one or more of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and mercaptopropanol.
5. The machine-made sand regulator of the alcohol ether modified carboxylic acid polymer is characterized in that: the method according to claim 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200198143A1 (en) * | 2018-12-19 | 2020-06-25 | Pearson Packaging Systems | Knocked-Down Case Inspection and Erection Method |
| CN112661914A (en) * | 2021-01-15 | 2021-04-16 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | Novel polycarboxylate superplasticizer special for machine-made sand and preparation method thereof |
| CN112724332A (en) * | 2021-02-08 | 2021-04-30 | 湖北工业大学 | Polymer for high-impermeability concrete and preparation method thereof |
| CN112897933A (en) * | 2021-04-21 | 2021-06-04 | 深圳市天祥新材料有限公司 | Machine-made sand regulator for concrete |
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- 2021-07-26 CN CN202110843153.2A patent/CN113603827B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200198143A1 (en) * | 2018-12-19 | 2020-06-25 | Pearson Packaging Systems | Knocked-Down Case Inspection and Erection Method |
| CN112661914A (en) * | 2021-01-15 | 2021-04-16 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | Novel polycarboxylate superplasticizer special for machine-made sand and preparation method thereof |
| CN112724332A (en) * | 2021-02-08 | 2021-04-30 | 湖北工业大学 | Polymer for high-impermeability concrete and preparation method thereof |
| CN112897933A (en) * | 2021-04-21 | 2021-06-04 | 深圳市天祥新材料有限公司 | Machine-made sand regulator for concrete |
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